Silver halide color photographic material containing a 1h-pyrazole (3,2-C)-s-triazole derived magenta coupler

ABSTRACT

A silver halide color photographic material having at least one silver halide emulsion layer on a support is disclosed. Said silver halide emulsion layer contains at least one of the 1H-pyrazolo [3,2-c]-S-triazole derived magenta couplers that have a substituent of the following formula at 3-position: 
     
         --R.sub.1 --S(O).sub.n --R.sub.2 
    
     wherein 
     R 1  is an alkylene group; 
     R 2  is an alkyl, cycloalkyl or aryl group; and 
     n is 1 or 2.

This application is a continuation of application Ser. No. 086,188,filed Aug. 14, 1987, now abandoned which in turn is a continuation ofapplication Ser. No. 775,685, filed Sept. 13, 1985 now abandoned.

FIELD OF THE INVENTION

The present invention relates to a silver halide color photographicmaterial that contains a magenta coupler capable of effective colorformation and which forms a magenta dye image having improved keepingquality, particularly in terms of light fastness. More specifically, theinvention relates to a silver halide color photographic materialcontaining a novel 1H-pyrazolo[3,2-c]-S-triazole derived magentacoupler.

BACKGROUND OF THE INVENTION

The formation of dye images in most silver halide color photographicmaterials depends on the reduction of exposed silver halide grains withan aromatic primary amine color developing agent and the subsequentcoupling of the resultant oxidation product of the color developingagent with couplers that respectively form yellow, magenta and cyandyes.

Pyrazolone type couplers are commercially used as couplers for providingmagenta dyes, but they have an unwanted secondary absorption and theirkeeping quality, particularly their resistance to formalin gas, isrelatively low.

A variety of 1H-pyrazol[3,2-c]-S-triazole derived magenta couplers havebeen proposed to overcome these problems of the conventional pyrazolonetype couplers. Reference should be had to U.S. Pat. No. 3,725,067, aswell as British Pat. Nos. 1,252,418 and 1,334,515. The compoundsdisclosed in these patents avoid the problem of secondary absorption butthe improvement is inadequate in terms of resistance to formalin gas andis insignificant in respect of the production of a light-fast magentadye image. The compound disclosed in Research Disclosure No. 12443 hasno commercial value because of its low color formation. The1H-pyrazolo[3,2-c]-S-triazole type magenta coupler disclosed inUnexamined Published Japanese Patent Application No. 42045/1983 featuressignificant improvements in formalin resistance and color formation butlittle improvement has been achieved in terms of the production of alight-fast image.

Improved color development has also been achieved by the couplersdescribed in Unexamined Published Japanese Patent Application Nos.99437/1984 and 125732/1984 but the dye images produced by these couplersare still low in light fastness. The coupler disclosed in UnexaminedPublished Japanese Patent Application No. 99437/1984 depends on theconcomitant use of additives for providing a light-fast image. Thecoupler disclosed as Compound No. 19 in Unexamined Published JapanesePatent Application No. 125732/1984 produces a dye image having slightlyimproved light fastness but the improvement is far from beingsatisfactory.

In short, the 1H-pyrazolo[3,2-c]-S-triazole derived magenta couplersthat have been considered useful because of the absence of secondaryabsorption and their high resistance to formalin gas fall far short ofsatisfying the requirement for providing dye images with improved lightfastness.

SUMMARY OF THE INVENTION

One object, therefore, of the present invention is to provide a silverhalide color photographic material that contains a magenta couplercapable of effective color formation and which forms a magenta dye imagehaving improved light fastness and resistance to formalin gas.

Another object of the invention is to provide a silver halide colorphotographic material that forms a magenta dye having improved spectralabsorption characteristics.

These objects of the invention are achieved by a silver halide colorphotographic material that has at least one silver halide emulsion layeron a support, said silver halide emulsion layer containing at least oneof the 1H-pyrazolo[3,2-c]-S-triazole derived magenta couplers that havea substituent of the following formula at 3-position:

    --R.sub.1 --S(0).sub.N --R.sub.2

wherein

R₁ is an alkylene group;

R₂ is an alkyl, cycloalkyl or aryl group;

n is 1 or 2, preferably 2.

DETAILED DESCRIPTION OF THE INVENTION

The inventors have found that compounds wherein a group represented bythe above formula is substituted at 3-position of1H-pyrazolo[3,2-c]-S-triazole will exhibit effective color formation andprovide magenta dye images having improved light fastness and formalinresistance.

Further improvements in light fastness and color formation are achievedby introducing as a substituent a leaving group other than hydrogen at7-position of 1H-pyrazolo[3,2-c]-S-triazole which is the site ofcoupling with the oxidation product of a color developing agent.

The alkylene group at R₁ may be substituted by alkyl, aryl (e.g.phenyl), halogen, cyano, a group that is bonded by carbonyl (e.g.alkoxycarbonyl, acyl or carbamoyl), or a group that is bonded by ahetero atom (e.g. nitro, alkoxy, alkylthio or dialkylamino). Thealkylene group at R₁ preferably has 1 to 6 carbon atoms.

The alkyl group at R₂ includes a primary alkyl, a branched alkyl(secondary or tertiary alkyl). The primary alkyl is an alkyl having twohydrogen atoms attached to the carbon atom directly coupled to themagenta coupler of the present invention; the secondary alkyl is analkyl having one hydrogen atom attached to the carbon having asubstituent; and the tertiary alkyl is an alkyl having no hydrogen atomattached to the carbon atom directly coupled to the magenta coupler ofthe present invention. The alkyl group as R₂ may be linear or branchedand preferably has 1-30 carbon atoms as illustrated by methyl, ethyl,propyl, i-propyl, butyl, 2-ethylhexyl, octyl, dodecyl, tetradecyl,hexadecyl, octadecyl and 2-hexyldecyl. An example of the cycloalkylgroup as R₂ is cyclohexyl. The alkyl or cycloalky group represented byR₂ may have a substituent such as an aryl group, heterocyclic group,halogen atom or a cyano group; a substituent that is bonded by carbonylas illustrated by alkoxycarbonyl, acyl or carbamoyl; or a substituentthat is bonded by a hetero atom (e.g. O, N or S) as illustrated bynitro, alkoxy, alkylthio, alkylsulfonyl, arylsulfonyl, alkylsulfinyl,arysulfinyl or dialkylamino. If two or more of these substituents arepresent, they may be the same or different. If the heterocyclic group isa 1H-pyrazolo[3,2-c]-S-triazole-3 -yl compound, a bis type1H-pyrazolo[3,2-c]-S-triazole compound is formed and this is of course amagenta coupler included within the scope of the present invention.

Examples of the leaving group other than hydrogen that may be bonded tothe 7-position coupling site include halogens and organic groups thatare bonded to the coupling site by an oxygen, nitrogen or sulfur atom.Illustrative leaving groups that are bonded to the coupling site by anoxygen atom include alkoxy, aryloxy, acyloxy and heterocyclic oxy;exemplary leaving groups that are bonded to the coupling site by anitrogen atom include acylamino, diacylamino, sulfonamido, and 5- or6-membered heterocyclic groups containing that nitrogen atom; andillustrative leaving groups that are bonded to the coupling site by asulfur atom include thiocyano, alkylthio, arylthio, heterocyclic thio,arylsulfonyl and alkylsulfonyl.

Compounds preferred for the purposes of the present invention arerepresented by the following formula: ##STR1## wherein R₁, R₂ and n arealready defined above; X is a leaving group which leaves upon reactionwith the oxidation product of a color developing agent and is alsodefined above.

The symbol R in the above formula represents an alkyl group, acycloalkyl group, an aryl group or a heterocyclic group. The alkyl groupmay be a primary alkyl or a branched secondary or tertiary alkyl. Thealkyl may have a substituent as illustrated in connection with thedefinition of R₂. If the alkyl as R is a secondary alkyl, it maypreferably have the following formula: ##STR2## wherein R₃ and R₄ areeach a halogen atom, a cyano group, a nitro group, an alkyl group, anaryl group, a heterocyclic group, or an alkyl, aryl or heterocyclicgroup that is bonded by an oxygen, nitrogen or sulfur atom, or an alkyl,aryl or heterocyclic group that is bonded by an acylamino, carbamoyl,sulfonamido, sulfamoyl, carbonyl, carbonyloxy, oxycarbonyl, ureido,thioureido, thioamido, sulfon or sulfonyloxy; R₃ and R₄ may combinetogether to form a carbon ring or a hetero ring.

Further description of R₃ and R₄ is given below. Examples of the halogenatom represented by R₃ or R₄ include Cl, Br and F. Examples of the alkylgroup represented by R₃ or R₄ include straight-chained or branched alkylgroups having 1 to 20 carbon atoms (e.g. methyl, ethyl, propyl,i-propyl, sec-butyl, n-butyl, t-butyl, n-octyl, t-octyl, dodecyl andoctadecyl). These groups may have substituents such as halogen atom,nitro, cyano, alkoxy, aryloxy, amino, acylamino, carbamoyl, sulfonamido,sulfamoyl, imido, alkylthio, arylthio, aryl, alkoxycarbonyl and acyl.Exemplary substituted alkyl groups include chloromethyl, bromomethyl,trichloromethyl, β-nitroethyl, δ-cyanobutyl, methoxymethyl, ethoxyethyl,phenoxyethyl, N-methylaminoethyl, dimethylaminobutyl, acetaminoethyl,benzoylamino, propyl, ethylcarbamoylethyl, methanesulfonamidoethyl,ethylthioethyl, p-methoxyphenylthiomethyl, p-chlorophenylmethyl,naphthylethyl, ethoxycarbonylethyl and acetylethyl.

Examples of the aryl group as R₃ or R₄ include phenyl and naphthyl,which may have substituents as listed in connection with the descriptionof the alkyl group.

Illustrative heterocyclic groups as R₃ or R₄ are 5- or 6-membered ringshaving at least one of nitrogen, oxygen and sulfur atoms and they may bearomatic or non-aromatic. Specific examples of the heterocyclic groupinclude pyridyl, quinolyl, pyrrolyl, morpholyl, furanyl,tetrahydrofuranyl, pyrazolyl, triazolyl, tetrazolyl, thiazolyl,oxazolyl, imidazolyl and thiadiazolyl. These heterocyclic groups mayhave substituents as listed in connection with the description of thealkyl group.

Examples of the carbon ring formed by combination of R₃ and R₄ includecyclopropyl, cyclopentyl, cyclohexyl and cyclohexenyl. Examples of thehetero ring that may be formed by R₃ as combined with R₄ includepiperidyl, pyrrolidyl, dioxanyl and morpholinyl.

Preferred aryl groups as R are substituted and unsubstituted phenylgroups. Specific examples of the heterocyclic group as R are furan ringand thiophene ring.

When R₂ is an alkyl group or a cycloalkyl group, R₁ is an alkylenegroup, which preferably has 3 to 6 carbon atoms in the straight chain.

The 1H-pyrazolo[3,2-c]-S-triazole derived magenta couplers in accordancewith the present invention are illustrated by, but by no means limitedto, the following compounds. Preferably, these couplers arenon-diffusible and have molecular weights not exceeding 450. ##STR3##

The synthesis of 1H-pyrazolo[3,2-c]-S-triazole after the introduction ofR₂ --S(O)_(n) --R₁ --COOH may be performed by reference to ResearchDisclosure No. 12443 and Journal of the Chemical Society, Ferkin I,1977, pp. 2047-2052. The introduction of a leaving group at the7-position coupling site may be performed by reference to U.S. Pat. No.3,725,067 and Unexamined Published Japanese Patent Application No.99437/1984.

The group R₂ --SO₂ --R₁ -COOH is obtained by oxidizing the correspondingR₂ --S--R₁ -COOH with hydrogen peroxide in accordance with the methoddescribed in Unexamined Japanese Patent Application No. 24321/1972. Thegroup R₂ --SO--R₁ --COOH is obtained by reacting equimolar amounts of R₂--S--R₁ --COOH and hydrogen peroxide under cooling.

Synthesis of Magenta Coupler (1)

The reaction scheme is shown below: ##STR4##

(1) Synthesis Compound (I)

This compound was prepared by the method described in Journal of theChemical Society, Perkin I, 1977, pp. 2047-2052.

(2) Synthesis of Compound (II)

Ninety-two grams of (I) was dispersed in 1,000 ml of acetonitrile. Tothe dispersion, 60 g of triethylamine was added and acid chlorideprepared by reacting 222 g of acid with thionyl chloride was addeddropwise to the mixture under refluxing. The resulting mixture wasrefluxed for an additional 30 minutes. After cooling the mixture, thecrystal was recovered by filtration, washed with water thoroughly anddried. The end compound was obtained in a yield of 80%.

(3) Synthesis of Compound (III)

To 1,500 ml of toluene, 193 g of (II) and 53.5 g of phosphorusoxychloride were added and the mixture was refluxed for 5 hours.Thereafter, the toluene was distilled off and 1,500 ml of acetonitrileand 80 g of pyridine were added to the residue and the resulting mixturewas refluxed for an additional 1.5 hours. After distilling off theacetonitrile, water was added to the residue and the resultant crystalwas recovered by filtration. The crystal was washed with water, driedand recrystallized from acetonitrile to give the end compound (III).

(4) Synthesis of Compound (IV)

One hundred and thirty grams of (III) was added to a mixture of glacialacetic acid (1,000 ml), concentrated sulfuric acid (100 ml) and water(20 ml) and the resultant mixture was refluxed for 10 hours. Afterleaving the mixture to cool down, an aqueous caustic soda solutionconsisting of 1,000 ml of water and 180 g of caustic soda was addedunder agitation. The resulting crystal was recovered by filtration,washed thoroughly with water, and dried to give the end compound (IV).

(5) Synthesis of Compound (1)

Twenty grams of (IV) was dissolved in chloroform, and to the solution,an equivalent amount of N-chlorosuccinimide was added. The mixture washeld at room temperature for 1 hour to perform reaction. The reactionmixture was washed with dilute alkali and subjected to further washingwith water. The chloroform was distilled off and the residue waspurified by column chromatography on silica gel using benzene-acetone asa solvent. The purified residue was identified as the end compound byNMR spectrum and mass spectrum.

Synthesis of Magenta Coupler (47)

The synthesis scheme is shown below: ##STR5##

(1) Synthesis of Compound A

A mixture of octadecylcaptan (28.6 g) and α-methyl-γ-butyrolactone (10g) was dissolved in dimethylformamide (200 ml), and after addition of28% aqueous sodium methylate (19.3 g), the mixture was heated at 80° C.for 2 hours under agitation. After the reaction, the mixture was pouredinto water and rendered acidic with hydrochloric acid.

The resulting crystal was recovered by filtration and washed withmethanol to provide 38.6 g of compound A. This was used in thesubsequent step of reaction without purification.

(2) Synthesis of Compound B

Compound A (38.6 g) was dissolved in acetic acid (200 ml) and to thesolution, 25.4 g of 35% H₂ O₂ was slowly added dropwise at 60°-70° C.After the reaction, the mixture was cooled and the resulting crystal wasrecovered by filtration. After washing with 80% methanol, the crystalwas recrystallized from methanol to obtain 26 g of compound B. m.p.109°-110° C.

(3) Synthesis of Compound D

In 200 ml of acetonitrile, 11.4 g of hydrazine compound (compound C) wasdissolved and, to the solution, 6.1 g of triethylamine was added and themixture was boiled under agitation. Acid chloride prepared from 25.8 gof the acid obtained in (2) was dissolved in a small amount ofacetonitrile and the solution was added dropwise to the stirredsolution.

Thereafter, the mixture was refluxed for 1 hour and cooled to causecrystallization. The crystal was recovered by filtration and washed withwater. After drying, the crystal was recrystallized from methanol toobtain 27.6 g of compound D. m.p. 125°-127° C.

(4) Synthesis of Compound E

Compound D (24.5 g) was dissolved in 150 ml of toluene and, to thesolution, 6.2 g of phosphorus oxychloride was added and the resultingmixture was refluxed for 3 hours. Thereafter, the mixture was cooled toroom temperature, and stirred for 10 minutes after addition oftriethylamine (12 g). The stirred mixture was washed with warm water andthe toluene was distilled off under vacuum. The residue was purified bycolumn chromatography and recrystallized from methanol to obtain 15.0 gof compound E. m.p. 78°-81° C.

(5) Synthesis of Compound F

Compound E (15.0 g) was added to a mixture of concentrated sulfuric acid(15 ml), glacial acetic acid (75 ml) and water (15 ml) and the resultantmixture was refluxed for 8 hours. After the reaction, the mixture waspoured into iced water having 30 g of sodium hydroxide dissolvedtherein. The crystal was recovered by filtration and, after thoroughwashing with water, recrystallized from methanol to provide 10.2 g ofcompound F. m.p. 98°-100° C.

(6) Synthesis of Magenta Coupler (47)

Compound F (10.0 g) was dissolved in 100 ml of chloroform and, to thesolution, 2.6 g of N-chlorosuccinimide was added and the mixture washeld at room temperature for 30 minutes. Thereafter, the reactionmixture was washed with water and the chloroform was distilled off. Theresidue was mixed with hexane and heated to cause crystallization. Thecrystal was recovered by filtration and recrystallized from methanol toprovide 6.8 g of the end compound. m.p. 57°-59° C.

Synthesis of Magenta Couplers (2), (6) and (10)

The 1H-pyrazolo[3,2-c]-S-triazole nucleus was prepared in accordancewith Research Disclosure No. 12443, and respective leaving groups wereintroduced by the procedures described in U.S. Pat. No. 3,725,067 andUnexamined Published Japanese Patent Application No. 99437/1984.

The 1H-pyrazolo[3,2-c]-S-triazole nucleus in other magenta couplers wasprepared as in the case of the synthesis of magenta coupler (1). Leavinggroups were introduced in magenta couplers (5), (15), (17), (18) and(19) by referring to the disclosure in U.S. Pat. No. 3,725,067 andUnexamined Published Japanese Patent Application No. 99437/1984.

The silver halide color photographic material of the present inventionmay contain conventional dye forming couplers.

Known open-chain ketomethylene couplers may be used as yellow-formingcouplers. Benzoylacetanilide and pivaloylacetanilide compounds areparticularly useful. Specific examples of the usable yellow formingcouplers are described in U.S. Pat. Nos. 2,875,057, 3,265,506,3,408,194, 3,551,155, 3,582,322, 3,725,072, and 3,891,445; German Pat.No. 1,547,868, German Patent Application (OLS) Nos. 2,219,917, 2,261,361and 2,414,006; British Pat. No. 1,425,020; Japanese Patent PublicationNo. 10783/1976, Unexamined Published Japanese Patent Application Nos.26133/1972, 73147/1983, 102036/1976, 6341/1975, 123342/1975,130442/1975, 21827/1976, 87650/1975, 82424/1977 and 115219/1977.

Usable cyan forming couplers are phenolic and naphtholic compounds.Specific examples are found in U.S. Pat. Nos. 2,369,929, 2,434,272,2,474,293, 2,521,908, 2,895,826, 3,034,892, 3,311,476, 3,458,315,3,476,563, 3,583,971, 3,591,383, 3,767,411 and 4,004,929; German PatentApplication (OLS) Nos. 2,414,830 and 2,454,329; and Unexamined PublishedJapanese Patent Application Nos. 59838/1973, 26034/1976, 5055/1973,146828/1976, 69624/1977 and 90932/1977.

As magenta forming couplers, one or more of the couplers prepared inaccordance with the present invention may be used. They may also be usedin combination with known magenta couplers such as pyrazolone compounds,indazolone compounds, cyanoacetyl compounds, pyrazolinobenzimidazolecompounds and pyrazolotriazole compounds. It should however beemphasized that at least one of the magenta couplers incorporated in thesilver halide color photographic material of the present invention mustbe the coupler defined in accordance with the invention.

The coupler of the present invention may also be used in combinationwith colored couplers capable of color correction, or developmentinhibitor releasing couplers (DIR couplers) that are effective forproducing improved image quality.

The magenta coupler of the present invention and the respective couplersassociated thereto may be introduced into silver halide emulsion layersby any known method such as one described in U.S. Pat. No. 2,322,027.For example, the couplers are dispersed in hydrophilic colloids afterbeing dissolved in high-boiling organic solvents or low-boiling organicsolvents. Examples of the former type include alkyl esters of phthalicacid (e.g., dibutyl phthalate and dioctyl phthalate), phosphate esters(e.g., diphenyl phosphate, triphenyl phosphate, tricresyl phosphate anddioctylbutyl phosphate), citrate esters (e.g., tributyl acetylcitrate),benzoate esters (e.g., octyl benzoate), alkylamides (e.g., diethyllaurylamide), aliphatic acid esters (e.g. dibutoxyethyl succinate anddioctyl azelate) and trimesic acid esters (e.g. tributyl trimesate). Thelow-boiling organic solvents are those which boil at between about 30°C. and 150° C., and examples are lower alkyl acetates (e.g. ethylacetate and butyl acetate), ethyl propionate, secondary butyl alcohol,methyl isobutyl ketone, β-ethoxyethyl acetate and methyl cellosolveacetate. The high-boiling organic solvents may be used in combinationwith the low-boiling organic solvents.

Dispersion methods using polymers may also be used and such methods aredescribed in Japanese Patent Publication No. 39853/1976 and UnexaminedPublished Japanese Patent Application No. 59943/1976.

The magenta coupler of the present invention is incorporated in a silverhalide emulsion layer usually in the amount of from 0.005 to 2 moles,preferably from 0.03 to 0.5 mole, per mole of silver halide.

The magenta coupler of the present invention forms a satisfactorilylight-fast dye image, but even higher light fastness may be obtained byusing an anti-fading agent or by overlaying the emulsion layer ofinterest with a layer containing an ultraviolet absorber.

Illustrative anti-fading agents include hydroquinone derivatives of thetype described in U.S. Pat. Nos. 2,360,290, 2,418,613, 2,673,314,2,701,197, 2,704,713, 2,728,659, 2,732,300, 2,735,765, 2,710,801 and2,816,028, as well as British Pat. No. 1,363,921; gallic acidderivatives as described in U.S. Pat. Nos. 3,457,079 and 3,069,262;p-alkoxyphenols of the type described in U.S. Pat. Nos. 2,735,765 and3,698,909, as well as Japanese Patent Publication No. 20977/1974 and6623/1977; p-oxyphenol derivatives of the type described in U.S. Pat.Nos. 3,432,300, 3,573,050, 3,574,627 and 3,764,337, as well asUnexamined Published Japanese Patent Application Nos. 35633/1977,147434/1977 and 152225/1977; and bisphenols as described in U.S. Pat.No. 3,700,455.

Exemplary ultraviolet absorbers include aryl-substituted benzotriazolecompounds as described in U.S. Pat. No. 3,533,794, 4-thiazolidonecompounds (as described in U.S. Pat. Nos. 3,314,794 and 3,352,681),benzophenone compounds (as described in Unexamined Published JapanesePatent Application No. 2784/1971), connamic acid ester compounds (asdescribed in U.S. Pat. Nos. 3,705,805 and 3,707,375), butadienecompounds (as described in U.S. Pat. No. 4,045,229), and benzoxidolecompounds (as described in U.S. Pat. No. 3,700,455). Other compoundsusable as UV absorbers are found in U.S. Pat. No. 3,499,762 andUnexamined Published Japanese Patent Application No. 48535/1979.

Any of the silver halides that are incorporated in conventional silverhalide emulsions may be used in the present invention and they includesilver bromide, silver chloride, silver iodobromide, silverchlorobromide and silver chloroiodobromide. In order to providesensitivity for the desired spectral wavelength region, the silverhalides used in the present invention may be spectrally sensitized bysuitable selected sensitizing dyes. Usable dyes include cyanine,merocyanine, complex cyanine, complex merocyanine, holopolar cyanine,hemicyanine, styryl and hemioxonole dyes.

Useful sensitizing dyes are described in, for example, German Pat. No.929,080, U.S. Pat. Nos. 2,231,658, 2,493,748, 2,503,776, 2,519,001,2,912,329, 3,656,959, 3,672,897, 3,694,217, 4,025,349 and 4,046,572;British Pat. No. 1,242,588; and Japanese Patent Publication Nos.14030/1969 and 24844/1977.

These sensitizing dyes may be used either individually or incombination. Combined sensitizing dyes are often used for the purpose ofsupersensitization, as typically described in U.S. Pat. Nos. 2,688,545,2,977,229, 3,397,060, 3,522,052, 3,527,641, 3,617,293, 3,628,964,3,666,480, 3,672,898, 3,679,428, 3,703,377, 3,769,301, 3,814,609,3,837,862 and 4,026,707; British Pat. Nos. 1,344,281 and 1,507,803;Japanese Patent Publication Nos. 4936/1968 and 12375/1978; andUnexamined Published Japanese Patent Application Nos. 110618/1977 and109925/1977.

The silver halide emulsion used in the present invention may incorporatea variety of known photographic additives such as those described inResearch Disclosure No. 17643.

The silver halide color photographic material of the present inventionmay use any support material that is properly selected from among knownmaterials depending on the specific object, such as plastic films,plastic laminated paper, baryta paper and synthetic paper.

The silver halide color photographic material of the invention may adoptany of the layer arrangements commonly used in the photographicindustry.

The so arranged silver halide color photographic material of theinvention is exposed and thereafter subjected to color development by avariety of photographic processing techniques. The color developer usedto process this photographic material may contain any of the knownaromatic primary amine color developing agents that are extensively usedin various color photographic processes. Such developing agents includeaminophenolic and p-phenylenediamine derivatives. These compounds aregenerally used in salt forms, such as hydrochlorides or sulfates, whichare stabler than the free state. These compounds are used inconcentrations that generally range from about 0.1 to about 30 g,preferably from about 1 g to about 1.5 g, per liter of the colordeveloper.

Illustrative aminophenolic developing agents include o-aminophenol,p-aminophenol, 5-amino-2-oxytoluene, 2-amino-3-oxytoluene, and2-oxy-3-amino-1,4-dimethylbenzene.

Particularly useful primary aromatic amino color developing agents areN,N'-dialkyl-p-phenylenediamine compounds wherein the alkyl or phenylgroup may have a suitable substituent. Among these compounds, thefollowing are particularly advantageous:N,N'-diethyl-p-phenylene-diamine hydrochloride,N-methyl-p-phenylenediamine hydrochloride,N,N'-dimethyl-p-phenylenediamine hydrochloride,2-amino-5-(N-ethyl-N-dodecylamino)-toluene,N-ethyl-N-β-methanesulfonamidoethyl-3-methyl-4-aminoaniline sulfate,N-ethyl-N-β-hydroxyethylaminoaniline,4-amino-3-methyl-N,N'-diethylaniline, and4-amino-N-(2-methoxyethyl)-N-ethyl-3-methylaniline-p-toluene sulfonate.

In addition to these primary aromatic amino color developing agents, thecolor developer used in the processing of the photographic material ofthe present invention may contain a variety of additives that arecommonly incorporated in color developers and such additives includealkali agents (e.g. sodium hydroxide, sodium carbonate and potassiumcarbonate), alkali metal sulfites, alkali metal bisulfites, alkali metalthiocyanates, alkali metal halides, benzyl alcohol, water softeners andthickeners. The pH of the color developer is usually at least 7 and mostgenerally ranges from about 10 to about 13.

After color development, the photographic material of the presentinvention is processed by a solution having the fixing ability. If thissolution is a fixing bath, its use is preceded by a bleaching step. Thebleaching bath used in the bleaching step or the bleaching agent used ina bleach-fixing bath is made of a metal complex salt of an organic acid.This metal complex salt has the ability not only to oxidize metallicsilver (i.e., formed as a result of development) into silver halide butalso to ensure complete color formation by a color former. The structureof this metal complex salt is such that an organic acid such as anaminopolycarboxylic acid, oxalic acid or citric acid is coordinated to ametal ion such as iron, cobalt or copper. The organic acids mostpreferred for use in forming metal complex salts are polycarboxylicacids or aminopolycarboxylic acids. The polycarboxylic acids oraminopolycarboxylic acids may be in the form of alkali metal salts,ammonium salts or water-soluble salts.

Typical examples of polycarboxylic acids or amino-polycarboxylic acidsare listed below:

(1) ethylenediaminetetraacetic acid;

(2) diethylenetriaminepentaacetic acid;

(3) ethylenediamine-N-(β-oxyethyl)-N,N',N'-triacetic acid;

(4) propylenediaminetetraacetic acid;

(5) nitrilotriacetic acid;

(6) cyclohexanediaminetetraacetic acid;

(7) iminodiacetic acid;

(8) dihydroxyethylglycincitric acid (or tartaric acid);

(9) ethyletherdiaminetetraacetic acid;

(10) glycoletherdiaminetetraacetic acid;

(11) ethylenediaminetetrapropionic acid;

(12) phenylenediaminetetraacetic acid;

(13) ethylenediaminetetraacetic acid disodium salt;

(14) ethylenediaminetetraacetic acid tetra (trimethylammonium) salt;

(15) ethylenediaminetetraacetic acid tetrasodium salt;

(16) diethylenetriaminepentaacetic acid pentasodium salt;

(17) ethylenediamine-N-(β-oxyethyl)-N,N',N'-triacetic acid sodium salt;

(18) propylenediaminetetraacetic acid sodium salt;

(19) nitrilotriacetic acid sodium salt; and

(20) cyclohexanediaminetetraacetic acid sodium salt.

In addition to metal complex salts of these organic acids which are usedas bleaching agents, the bleaching bath used in processing the colorphotographic material of the present invention may contain a variety ofadditives, and preferred additives are rehalogenating agents such asalkali or ammonium halides (e.g. potassium bromide, sodium bromide,sodium chloride and ammonium bromide), metal salts and chelating agents.Any other additives that are conventionally incorporated in bleachingbaths may also be used and they include pH buffers (e.g. borate,oxalate, acetate, carbonate and phosphate salts), alkylamines andpolyethylene oxides.

The fixing bath and bleach-fixing bath may also contain one or more pHbuffers that are selected from among sulfites (e.g. ammonium sulfite,potassium sulfite, ammonium bisulfite, potassium bisulfite, sodiumbisulfite, ammonium metabisulfite, potassium metabisulfite, and sodiummetabisulfite), and a variety of acids or salts (e.g. boric acid, borax,sodium hydroxide, potassium hydroxide, sodium carbonate, potassiumcarbonate, sodium bicarbonate, potassium bicarbonate, acetic acid,sodium acetate and ammonium hydroxide).

If the photographic material of the present invention is processed in ableach-fixing bath as it is supplied with a blix replenisher,thiosulfates, thiocyanates, sulfites or other salts may be incorporatedeither in the bleach-fixing bath or in the replenisher that is fed tosaid blix bath.

In order to increase the activity of the bleach-fixing bath used inprocessing the photographic material of the present invention, air oroxygen may be blown into a tank containing the bleach-fixing bath or itsreplenisher. Alternatively, a suitable oxidant such as hydrogenperoxide, bromate or persulfate may be added into the tank.

The following examples are provided for further illustration of theclaimed photographic material but are not to be construed as limitingthe invention.

EXAMPLE 1

One tenth of a mole, per mole of silver, of one of the magenta couplerslisted in Table 1 (which follows) was mixed with an equal weight oftricresyl phosphate and three times the coupler's weight of ethylacetate, and the mixture was heated to 60° C. to form a completesolution. The solution was then mixed with 1,200 ml of 5% aqueousgelatin solution containing 120 ml of a 5% aqueous solution of Alkanol B(trade name of du Pont for alkylnaphthalene sulfonate). The mixture wasemulsified with an ultrasonic disperser and the dispersion obtained wasadded to 4 kg of a green-sensitive silver iodobromide emulsion(containing 6 mol% AgI). To the mixture, 120 ml of a 2% solution (water:methanol=1:1) of 1,2-bis-(vinylsulfonyl)ethane was added as a hardener,and the so prepared coating solution was applied to a subbed transparentpolyester base, and the web was dried to provide a sample of colorphotographic material (with silver deposit of 20 mg/100 cm²). The othersamples were prepared by the same procedure.

Each of the samples thus prepared was subjected to exposure through anoptical wedge as in the conventional process and subsequently processedby the following scheme. The results of such photographic processing areshown in Table 1 below.

    ______________________________________                                        Processing scheme                                                             Steps         Temperature, °C.                                                                    Time                                               ______________________________________                                        Color development                                                                           38           3 min, 15 sec                                      Bleaching     38           4 min, 20 sec                                      Washing       38           3 min, 15 sec                                      Fixing        38           4 min, 20 sec                                      Washing       38           3 min, 15 sec                                      Stabilizing   38           1 min, 30 sec                                      Drying        47 to 55     16 min, 30 sec                                     ______________________________________                                    

The formulation of each of the processing solutions used is indicatedbelow.

    ______________________________________                                        Color developer                                                               Potassium carbonate      30     g                                             Sodium hydrogencarbonate 2.5    g                                             Potassium sulfite        5      g                                             Sodium bromide           1.3    g                                             Potassium iodide         2      mg                                            Hydroxylamine sulfate    2.5    g                                             Sodium chloride          0.6    g                                             Diethylenetriaminepentaacetic acid                                                                     2.5    g                                             sodium salt                                                                   4-amino-3-methyl-N--ethyl-N--(β-                                                                  4.8    g                                             hydroxyethyl)aniline sulfate                                                  Potassium hydroxide      1.2    g                                             Water to make            1,000  ml                                            pH adjusted to 10.06 by addition of                                           potassium hydroxide or 20% H.sub.2 SO.sub.4.                                  Bleaching bath                                                                Ethylenediaminetetraacetic acid iron                                                                   100    g                                             ammonium salt                                                                 Ethylenediaminetetraacetic acid                                                                        10     g                                             Ammonium bromide         150    g                                             Glacial acetic acid      40     ml                                            Sodium bromate           10     g                                             Water to make            1,000  ml                                            pH adjusted to 3.5 by addition of                                             ammonia water or glacial acetic acid.                                         Fixing bath                                                                   Ammonium thiosulfate     180    g                                             Anhydrous sodium sulfite 12     g                                             Sodium metabisulfite     2.5    g                                             Ethylenediaminetetraacetic acid                                                                        0.5    g                                             disodium salt                                                                 Sodium carbonate         10     g                                             Water to make            1,000  ml                                            Stabilizing bath                                                              Formalin (37% aq. sol.)  2      ml                                            Konidax (product of Konishiroku                                                                        5      ml                                            Photo Industry Co., Ltd.)                                                     Water to make            1,000  ml                                            ______________________________________                                    

                  TABLE 1                                                         ______________________________________                                        Sam-             Specific         Formalin                                                                             Light                                ple              sensi-   Maximum resis- fast-                                No.  Coupler used                                                                              tivity.sup.(1)                                                                         density tance.sup.(2)                                                                        ness.sup.(3)                         ______________________________________                                        1-11 Comparative 100      2.64    92     25                                        coupler 1                                                                1-12 Comparative  96      2.58    91     27                                        coupler 2                                                                1-13 Comparative 103      2.70    93     23                                        coupler 3                                                                1-14 Comparative 102      2.71    94     24                                        coupler 4                                                                1-15 Coupler (11)                                                                              100      2.63    90     35                                        of the invention                                                         1-16 Coupler (12)                                                                              101      2.65    92     34                                        of the invention                                                         1-17 Coupler (1)  99      2.58    93     39                                        of the invention                                                         1-18 Coupler (7) 102      2.75    91     40                                        of the invention                                                         1-19 Coupler (3) 105      2.81    93     37                                        of the invention                                                         1-20 Coupler (4) 110      2.92    90     35                                        of the invention                                                         1-21 Coupler (19)                                                                              108      2.90    92     33                                        of the invention                                                         ______________________________________                                         acl Notes

(1) The specific sensitivity is expressed as the reciprocal of theexposure that provides a fog plus 0.1 density, with the value for sampleNo. 11 (using comparative coupler 1) being taken as 100.

(2) A sample was subjected to color development after it was held for 3days in a sealed container of 0.9% aqueous formalin (6 ml) conditionedat 30° C. and 62% r.h. An untreated sample was also color developed. Theformalin resistance of the first sample was calculated by the followingformula: ##EQU1##

(3) A color-developed sample was illuminated in a xenon fadeometer for 5days and the percentage residual dye for the initial density (D) of 1.0was calculated to determine the lightfastness of the image: ##EQU2##

The data in Table 1 show that the couplers prepared in accordance withthe present invention were improved over the comparative couplers interms of color formation and the production of formalin-resistant andlight-fast dye images.

EXAMPLE 2

Sample Nos. 1-11 to 1-19 prepared in Example 1 were exposed through anoptical wedge and subsequently processed by the following scheme. Theresults are shown in Table 2. The specific sensitivity and lightfastness were measured by the same methods as used in Example 1.

    ______________________________________                                        Processing scheme:                                                            ______________________________________                                        Color development                                                                            38° C.                                                                              3 min., 30 sec                                    Bleach-fixing  33° C.                                                                              1 min., 30 sec                                    Stabilizing or 25-30° C.                                                                           3 min.                                            washing                                                                       Drying         75-80° C.                                                                           ca. 2 min.                                        ______________________________________                                    

The solutions used in this scheme had the following formulations.

    ______________________________________                                        Color developer                                                               Benzyl alcohol             15     ml                                          Ethylene glycol            15     ml                                          Potassium sulfite          2.0    g                                           Potassium bromide          0.7    g                                           Sodium chloride            0.2    g                                           Potassium carbonate        30.0   g                                           Hydroxylamine sulfate      3.0    g                                           Tripolyphosphoric acid (TPPS)                                                                            2.5    g                                           3-Methyl-4-amino-N--ethyl-N--(β-methane-                                                            5.5    g                                           sulfonamidoethyl)aniline sulfate                                              Brightener (4,4'-diaminostilbenzosulfonic                                                                1.0    g                                           acid derivative)                                                              Potassium hydroxide        2.0    g                                           Water to make              1,000  ml                                          pH adjusted to 10.20                                                          Bleachi-fixing bath                                                           Ethylenediaminetetraacetic acid iron                                                                     60     g                                           (III) ammonium dihydrate salt                                                 Ethylenediaminetetraacetic acid                                                                          3      g                                           Ammonium thiosulfate (70% aq. sol.)                                                                      100    ml                                          Ammonium sulfite (40% aq. sol.)                                                                          27.5   ml                                          pH adjusted to 7.1 by addition of potassium                                   carbonate or glacial acetic acid                                              Water to make              1,000  ml                                          Stabilizing bath                                                              5-Chloro-2-methyl-4-isothiazolin-3-one                                                                   1.0    g                                           Ethylene glycol            10     g                                           1-Hydroxyethylidene-1,1'-diphosphonic acid                                                               2.5    g                                           Bismuth chloride           0.2    g                                           Magnesium chloride         0.1    g                                           Ammonium hydroxide (28% aq. sol.)                                                                        2.0    g                                           Sodium nitrilotriacetate   1.0    g                                           Water to make              1,000  ml                                          pH adjusted to 7.0 by addition of                                             ammonium hydroxide or sulfuric acid.                                          ______________________________________                                    

                  TABLE 2                                                         ______________________________________                                        Sample             Specific  Maximum  Light                                   No.   Coupler used sensitivity                                                                             density  fastness                                ______________________________________                                        2-11  Comparative  100       2.41     24                                            coupler 1                                                               2-12  Comparative  100       2.42     26                                            coupler 2                                                               2-13  Comparative  105       2.51     23                                            coupler 3                                                               2-14  Comparative  108       2.52     25                                            coupler 4                                                               2-15  Coupler (11) of                                                                            101       2.42     37                                            the invention                                                           2-16  Coupler (12) of                                                                             99       2.39     38                                            the invention                                                           2-17  Coupler (1) of                                                                              77       2.39     36                                            the invention                                                           2-18  Coupler (7) of                                                                              98       2.38     40                                            the invention                                                           2-19  Coupler (3) of                                                                             102       2.43     37                                            the invention                                                           2-20  Coupler (4) of                                                                             105       2.50     38                                            the invention                                                           2-21  Coupler (19) of                                                                            104       2.48     34                                            the invention                                                           ______________________________________                                    

EXAMPLE 3

A sample of silver halide color photographic material was prepared bycoating the following layers in sequence on a support made ofpolyethylene coated paper containing anatase type TiO₂. The amounts ofthe additives incorporated in each of the layers described below arebased on an area of 100 cm².

(1) Layer containing 20 mg of gelatin, 5 mg in terms of silver of ablue-sensitive silver chlorobromide emulsion, and 3 mg of dioctylphthalate coupler solvent having dissolved the resin 8 mg of Y-coupler*and 0.1 mg of 2,5-di-t-octylhydroquinone:

(2) Interlayer containing 12 mg of gelatin, and 2 mg of dibutylphthalate UV absorber solvent having 0.5 mg 2,5-di-t-octylhydroquinoneand 4 mg of UV absorber* dissolved therein:

(3) Layer containing 18 mg of gelatin, 4 mg in terms of silver of agreen-sensitive silver chlorobromide emulsion, and 2.5 mg of dioctylphthalate coupler solvent having dissolved therein 5 mg of M-coupler*, 2mg of antioxidant* and 0.2 mg of 2,5-di-t-octylhydroquinone:

(4) Interlayer having the same composition as (2):

(5) Layer containing 16 mg of gelatin, 4 mg in terms of silver of ared-sensitive silver chlorobromide emulsion, and 2.0 mg of tricresylphosphate coupler solvent having dissolved therein 3.5 mg of C-coupler*and 0.1 mg of 2,5-di-t-octyl-hydroquinone:

(6) Gelatin protective layer containing 9 mg of gelatin.

Each of the layers (1) to (6) also contained a coating aid, while layers(4) to (6) further contained a gelatin crosslinking agent. Theultraviolet absorber used in each of the layers (2) and (4) was amixture of UV-1 and UV-2 having the structures shown below. Theantioxidant incorporated in layer (3) wasdi-t-pentylhydroquinone-di-octyl ether.

Eleven samples of multi-layered photographic material were prepared asabove and each was processed as in Example 2. The specific types of theY-coupler, M-coupler and C-coupler used, and the results of thephotographic processing are shown in Table 3 below. Each of the sampleswas checked for its magenta density after exposure to white light. Thespecific sensitivity and light fastness were measured by the samemethods as used in Example 1. The data in Table 3 show the improvedlight fastness of the dye images produced by using the magenta couplersprepared in accordance with the present invention. It was also clearthat the light fastness of the images could be further improved by usingUV absorbers in combination with the magenta couplers. ##STR6##

                                      TABLE 3                                     __________________________________________________________________________    Sample                                                                            Layer (1)                                                                           Layer (3)                                                                             Layer (5)    Specific                                                                            Maximum                                                                             Light                              No. Y-coupler                                                                           M-coupler                                                                             C-coupler                                                                           UV-absorber                                                                          sensitivity                                                                         density                                                                             fastness                                                                          Remarks                        __________________________________________________________________________    3-31                                                                              Y-1   Comparative                                                                           C-1   --     100   2.30  22                                           coupler (1)                                                         3-32                                                                              Y-1   Comparative                                                                           C-1   UV-1   101   2.27  35  2 mg of UV                               coupler (1)   UV-2                   absorber in                                                                   layer (5)                      3-33                                                                              Y-1   Coupler (12)                                                                          C-1   --      99   2.30  39                                           of the invention                                                    3-34                                                                              Y-1   Coupler (12)                                                                          C-1   UV-1   102   2.26  50                                           of the invention                                                                            UV-2                                                  3-35                                                                              Y-2   Coupler (12)                                                                          C-2   UV-1   102   2.35  49                                           of the invention                                                                            UV-2                                                  3-36                                                                              Y-2   Coupler (12)                                                                          C-2   UV-1   101   2.38  57  Another layer (2)                        of the invention                                                                            UV-2                   inserted between                                                              layers (5) and (6)                                                            in sample No. 35               3-37                                                                              Y-1   Coupler (12)                                                                          C-3   UV-1   103   2.39  48                                           of the invention                                                                            UV-2                                                  3-38                                                                              Y-1   Coupler (12)                                                                          C-3   UV-1    99   2.32  56  Same layer arrange-                      of the invention                                                                            UV-2                   ment as in Sample                                                             No. 36                         3-39                                                                              T-2   Coupler (12)                                                                          C-4   UV-1    97   2.32  47                                           of the invention                                                                            UV-2                                                  3-40                                                                              Y-2   Coupler (12)                                                                          C-1   UV-1   103   2.35  47                                           of the invention                                                                            UV-2                                                  3-41                                                                              Y-1   Coupler (11)                                                                          C-1   UV-1   102   2.37  51                                           of the invention                                                                            UV-2                                                  __________________________________________________________________________

What is claimed is:
 1. A silver halide color photographic materialhaving at least one silver halide emulsion layer on a support, saidsilver halide emulsion layer containing at least one of the1H-pyrazolo[3,2-c]-S-triazole derived magenta couplers that have asubstituent of the following formula at 3-position:

    --R.sub.1 --S(O).sub.n --R.sub.2

wherein R₁ is an alkylene group; R₂ is an alkyl, cycloalkyl or arylgroup; and n is 1 or
 2. 2. A silver halide color photographic materialaccording to claim 1, wherein said magenta coupler is one represented bythe following formula: ##STR7## wherein R₁ is an alkylene group;R₂ is analkyl, cycloalkyl or aryl group; X is a leaving group which leaves uponreaction with the oxidation product of a color developing agent; R is analkyl, cycloalkyl, aryl or heterocyclic group; and N is 1 or
 2. 3. Asilver halide color photographic material according to claim 2, whereinthe alkyl group represented by R is a tertiary alkyl group.
 4. A silverhalide color photographic material according to claim 2, wherein thealkyl group represented by R is a tertiary butyl group.
 5. A silverhalide color photographic material according to claim 1, wherein n inthe formula for said substituent is
 1. 6. A silver halide colorphotographic material according to claim 2, wherein R in the formula forsaid magenta coupler is a secondary alkyl group, R₁ is an alkylene grouphaving 3 to 6 carbon atoms in the straight chain, n is 2 and R₂ is analkyl or cycloalkyl group.
 7. A silver halide color photographicmaterial according to claim 2, wherein X in the formula for said magentacoupler is a halogen atom.
 8. A silver halide color photographicmaterial according to claim 1, wherein said magenta coupler is thefollowing compound: ##STR8##
 9. A silver halide color photographicmaterial according to claim 1, wherein said magenta coupler is oneselected from among the following three compounds: ##STR9##
 10. A silverhalide color photographic material according to claim 1, wherein R₁ isan alkylene group having 1 to 6 carbon atoms.
 11. A silver halide colorphotographic material according to claim 1, wherein R₂ is an alkyl oraryl group.